Victoria Lachkova

SYNTHESIS OF 1-METHYL-1-(N-SUBSTITUTED CARBAMOYL- AND THIOCARBAMOYL-AMINO) ALKANEPHOSPHONIC ACIDS-DIETHYL ESTERS

Abstract Diethylesters of 1-methyl-1-(N-substituted carbamoyl- or thiocarbamoyl-amino)-alkane-phosphonic acids are obtained by interaction of O,O-diethyl esters of 1-amino-1-methyl-alkanephosphonic acids and different isocyanates or isothiocyanates at room temperature. Cyclization of 1-methyl-I-(N-butylcarbamoyl-amino)-ethanephosphonic acid diethyl ester to 3-butyl-5,5,-dimethyl-2,4-dioxo-4-hydroxy-1,3,4-diazaphosphole is achieved.

INTERACTION BETWEEN PHENYLMETHANEPHOSPHONIC ACID DIETHYL ESTER AND ISOTHIOCYANATES

Abstract Diethyl esters of 1-N-substituted thioamido-phenylmethanephosphonic acids are obtained from 0,0-diethyl phenylmethanephosphonate, sodium amide as a metallation agent and alkyl- or arylisothiocyanates. It is established that parallel reactions also occur, resulting in the formation of the respective 1,3-disubstituted thioureas and 0-ethylthiocarbamates. These represent the main reaction products in the cases when ethanephosphonic acid diethyl ester is used as a starting reagent.

Coordination chemistry of a para-tert-octylcalix[4]arene fitted with phosphinoyl pendant arms towards 4f-elements: Extraction, synergism, separation

Abstract The solvent extraction of trivalent lanthanoids (Ln3+) by 5,11,17,23-tetra(para-tert-octyl)-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene (S), bearing four phosphine oxide donor groups at the lower rim as synergistic agent in combination with a 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP) in CHCl3 from chloride medium at µ = 0.1 was quantitatively described in the form of LnP3·S complexes. The role of the synergistic agent on the extraction process was discussed. The values of the separation factors have been evaluated. On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid mixed complex of Eu(III) with HP and S were proposed.

CARBAMOYL AND THIOCARBAMOYL DERIVATIVES OF AMINOMETHYL-DIMETYL-PHOSPHINE OXIDE

Abstract A group of N-substituted carbamoyl-and thiocarbamoyl-aminomethyl-dimethyl-phosphine oxides 1–9 have been synthesized. These compounds were prepared via reaction of aminomethyl-dimethyl-phosphine oxide with the corresponding isocyanates and isothiocyanates. The composition of the new compounds was proved by elemental analysis of nitrogen and their structure was confirmed by IR, 1H and 31P{H} MNR spectroscopy and mass spectrometry.

Synthesis and Characterization of Partially Substituted at Lower Rim Phosphorus Containing Calix(4)arenes

The synthesis and characterization of several new phosphorus-containing partially lower rim substituted derivatives of 5,11,17,23-tetra(t-butyl) calix(4)arene (I) and 5,11,17,23-tetra(t-octyl)calix(4)arene (II), namely 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(diphenylphosphinoyl-oxy) calix(4)arene (IV); 5,11,17,23-tetra(t-butyl)-25-hydroxy-26,27,28-tris(tetramethyldiamido-phosphinoyl-oxy) calix(4)arene (Vb); 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VI); 5,11,17,23-tetra (t-octyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VII) are reported. The structure of the synthesized calix(4)arene derivatives are identified and confirmed by elemental analysis, IR, 1H, 13C, 31P{1H} NMR spectroscopy and mass spectrometry as and X-ray crystallographic analysis of 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene VI. According to the NMR spectra, all calix(4)arenes are in cone conformation.

(CARBAMOYLAMINOPHENOXYMETHYL)-DIMETHYLPHOSPHINE OXIDES AND CORRESPONDING THIOCARBAMOYL DERIVATIVES

Abstract A group of (carbamoylaminophenoxymethyl)-dimethylphosphine oxides 1–13 and corresponding thiocarbarnoyl derivatives 14–26 were prepared via reaction of 2-, 3-and 4-(dimeth-ylphosphinylmethoxy)-phenylamines with isocyanates and isothiocyanates resp., The composition of the new compounds was confirmed by elemental analysis, IR, 1H and 31P{1HJ} MNR spectroscopy.

N-Dimethylphosphinoyl-substituted Aminomethanephosphonic Acids

Three new N-phosphinoyl-substituted aminomethanephosphonic acids have been synthesized and characterized: dimethylphosphinoylmethyl-imino-bis(methanephosphonic acid) (1), [3-(dimethylphosphinoyl)-propyl]-imino-bis(methanephosphonic acid) (2), and N-benzyl-Ndimethylphosphinoylmethyl- aminomethanephosphonic acid (3). The latter was isolated as a hydrochloride 3 ・ HCl. The acids have been prepared via Moedritzer-Irani reaction from the corresponding dimethylphosphinoyl-substituted primary and secondary aliphatic amines. Their structures have been confirmed by elemental analysis, IR, 1H, 31P{1H}, 13C{1H} NMR spectroscopy, electrospray ionization mass spectrometry, and single-crystal X-ray diffraction. Graphical Abstract N-Dimethylphosphinoyl-substituted Aminomethanephosphonic Acids

Carbamoyl and Thiocarbamoyl Derivatives of 3-Aminopropyl-dimethyl-phosphine Oxide

A series of fourteen new 3-[N-substituted carbamoyl (or thiocarbamoyl)]-aminopropyl-dimethyl-phosphine oxides have been synthesized and characterized. The compounds were prepared via reaction of the 3-aminopropyl-dimethyl-phosphine oxide with the corresponding isocyanates or isothiocyanates. The composition of the compounds was proved by elemental analysis and the structures were confirmed by IR, 1H, 31P, 31P{1H} NMR spectroscopy and by mass spectrometry. The structures of 3[(N-phenyl-thiocarbamoyl)amino]propyl-dimethyl-phosphine oxide (5), 3[(N-4- chlorophenyl-thiocarbamoyl)amino]propyl-dimethyl-phosphine oxide (6), and 3[(N-benzyl-thiocarbamoyl) amino]propyl-dimethyl-phosphine oxide (9) have been confirmed by X-ray diffraction.

STUDY ON THE KINETICS OF THE REACTION BETWEEN DIETHYL ESTER OF 1-AMINO-METHYL-ETHANEPHOSPHONIC ACID AND PHENYL ISOCYANATE

Abstract The kinetics of the reaction between O,O-diethyl ester of 1-amino-1-methyl-ethane phosphonic acid and phenylisocyanate, producing diethyl ester of 1-methyl-1-(N-phenylcarbamoyl-amino)ethane phosphonic acid is studied by IR spectroscopy. It is established that the reaction is of second order. The probable scheme of the reaction mechanism is suggested. The rate constant k of the initial stage of the reaction is determined. It is established that the rate constant is increased at the advanced stage of the process. The observed enhancement is ascribed to the autocatalytic effect of the reaction product.